JP2019151105A - Hard coat laminate film - Google Patents

Abstract

To provide a hard coat laminate film excellent in ball falling impact resistance, and capable of suitably being used as a member of an image display device, especially a display face plate of a smart phone or a tablet terminal.SOLUTION: A hard coat laminate film has a first hard coat 1, a second hard coat 2, and a transparent resin film in this order from a surface side, the first hard coat 1 consists of a coating containing no inorganic particle, the second hard coat 2 consists of a coating containing one or more (meth)acrylate such as polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in a molecule, a compound having two or more secondary thiol groups in a molecule, (meth)acrylate having two (meth)acryloyl groups in a molecule, and an inorganic fine particle with average particle diameter of 1 to 300 nm.SELECTED DRAWING: Figure 1

Description

The present invention relates to a novel hard coat laminated film. More specifically, the present invention preferably relates to a hard coat laminated film excellent in falling ball impact resistance.

In recent years, touch panels that are installed on image display devices such as a liquid crystal display, a plasma display, and an electroluminescence display and can be input by touching with a finger or a pen while watching the display have become widespread.

Conventionally, glass-based articles have been used for display faceplates of touch panels because they meet required characteristics such as heat resistance, dimensional stability, high transparency, high surface hardness, and high rigidity. On the other hand, glass has problems such as low impact resistance and easy cracking; low workability; difficult to handle; high specific gravity and heavy; difficult to meet demands for curved display and flexibility. Therefore, materials that replace glass have been actively studied, and hard coats with excellent surface hardness and scratch resistance on the surface of transparent resin films such as triacetylcellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene polymers. A large number of hard coat laminated films formed with a film have been proposed (for example, Patent Documents 1 to 4). However, smartphones and tablet devices are often accidentally dropped during use, and as a countermeasure against this, hard coat laminated films are expected to exhibit very high performance in the falling ball impact test. .

JP, 2006-060839, A JP 2014-152237 A JP 2008-201864 A Japanese Patent No. 5870222

An object of the present invention is to provide a novel hard coat laminated film, preferably to provide a hard coat laminated film having excellent falling ball impact resistance. Further problems of the present invention are excellent in falling ball impact resistance, surface hardness, transparency, scratch resistance, bending resistance, color tone, surface appearance, interlayer adhesion strength, and cutting workability, liquid crystal display, plasma display, and Providing hard coat laminated films suitable as members of image display devices such as electroluminescence displays (including image display devices having a touch panel function and image display devices not having a touch panel function), particularly display face plates of smartphones and tablet terminals There is to do. Still another object of the present invention is to provide a member of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display, in which both falling ball impact resistance and surface hardness are balanced at a high level, particularly smartphones and tablet terminals. The object is to provide a hard coat laminated film suitable as a display face plate.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by a specific hard coat laminated film.

That is, this invention has a 1st hard coat, a 2nd hard coat, and the layer of a transparent resin film in order from the surface side, The said 1st hard coat is,
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(D) 100 mass parts of polymerizable compound; and (E) 50-300 mass parts of inorganic fine particles having an average particle diameter of 1-300 nm;
Made of paint containing;
Here, the polymerizable compound (D) is
(D1) Polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule 60 to 30% by mass;
(D2) 5 to 70% by mass of a compound having two or more secondary thiol groups in one molecule; and
(D3) A group consisting of (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth) acrylate. One or more (meth) acrylates selected from 0 to 50% by weight;
The sum of the component (d1), the component (d2), and the component (d3) is 100% by mass;
It is a hard coat laminated film.

2nd invention has a layer of the 1st hard coat, the 2nd hard coat, and a transparent resin film in order from the surface side,
The first hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(D) 100 mass parts of polymerizable compound; and (E) 50-300 mass parts of inorganic fine particles having an average particle diameter of 1-300 nm;
Made of paint containing;
Here, the polymerizable compound (D) is
(D1) a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule; and
(D2) a compound having two or more secondary thiol groups in one molecule;
A hard coat laminated film comprising:

A third invention is the hard coat laminated film according to the first invention or the second invention, wherein the component (d2) contains a compound having two or three secondary thiol groups in one molecule. .

4th invention is a hard coat laminated film as described in 1st invention whose quantity of the said component (d3) in the said (D) polymeric compound is 5-50 mass%.

5th invention has a layer of the 1st hard coat, the 2nd hard coat, and a transparent resin film in order from the surface side,
The first hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(D) 100 mass parts of polymerizable compound; and (E) 50-300 mass parts of inorganic fine particles having an average particle diameter of 1-300 nm;
Made of paint containing;
Here, the polymerizable compound (D) is
(D1) a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule;
(D2) a compound having two or more secondary thiol groups in one molecule; and
(D3) A group consisting of (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth) acrylate. One or more (meth) acrylates selected from:
A hard coat laminated film comprising:

A sixth invention is the hard coat according to the fourth or fifth invention, wherein the component (d3) contains an aliphatic urethane (meth) acrylate having two (meth) acryloyl groups in one molecule. It is a laminated film.

A seventh invention is the hard coat laminated film according to the fourth invention or the fifth invention, wherein the component (d3) contains tricyclodecane dimethanol di (meth) acrylate.

The eighth invention is the hard coat laminated film according to any one of claims 4 to 7, wherein the component (d2) contains a compound having two or three secondary thiol groups in one molecule. is there.

9th invention has a layer of the 1st hard coat, the 2nd hard coat, and a transparent resin film in order from the surface side,
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a paint containing inorganic fine particles;
It is a hard coat laminated film satisfying the following characteristics (A) and (B).
(I) The surface opposite to the first hard coat surface of the hard coat laminated film and the float plate glass are bonded, and a steel ball having a mass of 110 g is freely dropped from a height of 30 cm onto the first hard coat surface. When visually observed from the first hard coat surface side, no trace of striking with a steel ball is observed.
(B) The pencil hardness of the surface of the first hard coat measured in accordance with JIS K 5600-5-4: 1999 is 3H or more except that the load is 1 kg.

In a tenth invention, the second hard coat is (d1) a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule; (d2) two or more 2 in one molecule. A hard coat laminated film according to the ninth invention, comprising a paint comprising: a compound having a secondary thiol group; and (E) inorganic fine particles having an average particle diameter of 1 to 300 nm.

In an eleventh aspect of the invention, the second hard coat is (d1) a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule; (d2) two or more 2 in one molecule. (D3) (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane The hard coat laminated film according to the ninth aspect of the present invention, comprising a paint comprising one or more (meth) acrylates selected from the group consisting of (meth) acrylates; and (E) inorganic fine particles having an average particle diameter of 1 to 300 nm. It is.

The twelfth invention is the hard coat laminated film according to any one of the ninth to eleventh inventions that further satisfy the following characteristics (c) and (d).
(C) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(D) The water contact angle after 20,000 cotton swabs on the first hard coat surface is 100 degrees or more.

A thirteenth invention is an image display device including the hard coat laminated film according to any one of the first to twelfth inventions.

A fourteenth invention is an article comprising the hard coat laminated film according to any one of the first to twelfth inventions.

The hard coat laminated film of the present invention is excellent in falling ball impact resistance. The preferred hard coat laminated film of the present invention is excellent in falling ball impact resistance, surface hardness, transparency, scratch resistance, bending resistance, color tone, surface appearance, interlayer adhesion strength, and machinability. Therefore, the hard coat laminated film of the present invention is a member of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display (including an image display device having a touch panel function and an image display device not having a touch panel function). In particular, it can be suitably used as a display face plate of a smartphone or tablet terminal. Another preferred hard coat laminated film of the present invention has a falling ball impact resistance and a surface hardness which are compatible at a high level. Therefore, the hard coat laminated film of the present invention can be suitably used as a member of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display, particularly as a display face plate of a smartphone or a tablet terminal.

In this specification, the term “film” is used as a term including a sheet. The term “resin” is used as a term including a resin mixture containing two or more resins and a resin composition containing components other than resins. Further, in this specification, laminating a certain layer and another layer in order means laminating those layers directly and interposing one or more other layers such as anchor coats between these layers. Including both lamination. The term “more than” relating to a numerical range is used in the sense of a certain numerical value or a certain numerical value. For example, 20% or more means 20% or more than 20%. The term “below” relating to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol “˜” relating to a numerical range is used to mean a certain numerical value, a certain numerical value and less than a certain other numerical value, or another certain numerical value. Here, it is assumed that some other numerical value is larger than a certain numerical value. For example, 10-90% means 10%, more than 10% and less than 90%, or 90%.

Unless otherwise specified, or unless otherwise specified, all numerical values used in the specification and claims are to be understood as being modified by the term “about”. Without attempting to limit the application of the doctrine of equivalents to the claims, each number should be interpreted in the light of significant figures and by applying conventional rounding techniques.

The hard coat laminated film of the present invention has a first hard coat layer, a second hard coat layer, and a transparent resin film layer in order from the surface side, and the first hard coat is made of a paint containing no inorganic particles; 2 Hard coat consists of the coating material containing an inorganic particle.

Inorganic particles (for example, silica (silicon dioxide); metal oxide particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, cerium oxide; magnesium fluoride , Metal fluoride particles such as sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles; etc.) are highly effective in increasing the hardness of the hard coat. On the other hand, the interaction with the resin component of the paint is weak, which has been a cause of insufficient falling ball impact resistance and scratch resistance. Therefore, in the present invention, the first hard coat that usually forms the outermost surface retains falling ball impact resistance and scratch resistance by not containing inorganic particles, while the second hard coat contains inorganic particles, Preferably, this problem is solved by increasing the hardness by including inorganic fine particles having an average particle diameter of 1 to 300 nm.

Here, “does not contain” inorganic particles means that it does not contain a significant amount of inorganic particles. In the field of hard coat forming paints, the significant amount of inorganic particles is usually about 1 part by mass or more with respect to 100 parts by mass of the resin component of the paint. Therefore, “does not contain” inorganic particles means that the amount of inorganic particles is usually less than 1 part by weight, preferably 0.1 parts by weight or less, more preferably 0.01 parts by weight with respect to 100 parts by weight of the resin component of the paint. It can be paraphrased as part or less.

Here, “containing” inorganic particles means that the particles contain a significant amount of inorganic particles to increase the hardness of the hard coat. In the field of hard coat forming paints, a significant amount for increasing the hardness of the hard coat is usually about 5 parts by mass or more with respect to 100 parts by mass of the resin component of the paint. Therefore, “containing” the inorganic particles means that the amount of the inorganic particles is usually 5 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably with respect to 100 parts by mass of the resin component of the paint. Can be paraphrased as 80 parts by mass or more, still more preferably 100 parts by mass or more, and most preferably 150 parts by mass or more.

First hard coat:
The first hard coat usually forms the surface of the hard coat laminated film of the present invention. The first hard coat forms a touch surface when the hard coat laminated film of the present invention is used as a display face plate of an image display device having a touch panel function. The first hard coat exhibits good scratch resistance and functions to maintain surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like.

In one embodiment, the first hard coat-forming coating material is not limited except that it does not contain inorganic particles, and any coating material can be used. Preferred examples of the first hard coat-forming coating material include an active energy ray-curable resin that can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. Can do.

Examples of the active energy ray-curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate Phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl ( (Meth) acrylate and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acrylo (Methoxy) acryloyl group-containing bifunctional reactive monomers such as 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) (Meth) acryloyl group-containing trifunctional reactive monomers such as acrylate and trimethylolethane tri (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; and dipenta Examples of the resin include one or more selected from (meth) acryloyl group-containing hexafunctional reactive monomers such as erythritol hexaacrylate, or resins having one or more of the above as constituent monomers. As said active energy ray curable resin, these 1 type, or 2 or more types of mixtures can be used. In the present specification, (meth) acrylate means acrylate or methacrylate.

When the hard coat laminated film of the present invention is used as a display face plate of an image display device having a touch panel function, particularly as a display face plate of a smartphone or tablet terminal, the falling ball impact resistance, surface hardness, transparency, scratch resistance, scratch resistance, From the viewpoints of bendability, color tone, surface appearance, interlayer adhesion strength, and machinability, the first hard coat-forming coating material includes (A) polyfunctional (meth) acrylate, (B) water repellent, and ( C) A paint containing a silane coupling agent and not containing inorganic particles is preferred. As said 1st hard-coat formation coating material, (A) Polyfunctional (meth) acrylate 100 mass parts; (B) Water repellent 0.01-7 mass parts; and (C) Silane coupling agent 0.01- More preferably, the coating material contains 10 parts by mass and does not contain inorganic particles.

(A) Polyfunctional (meth) acrylate:
The component (A) is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule, and has two or more (meth) acryloyl groups in one molecule. It is polymerized and cured by active energy rays such as to form a hard coat.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2, (Meth) acryloyl group-containing bifunctional reaction such as 2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane -Functional monomers; (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythritol (Meth) acryloyl group-containing tetrafunctional reactive monomers such as tetral (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth) acryloyl group containing tripentaerythritol acrylate Examples thereof include octafunctional reactive monomers and polymers (oligomers and prepolymers) containing one or more of these as constituent monomers. In the present specification, (meth) acrylate means acrylate or methacrylate.

The component (A) is preferably a (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule from the viewpoint of surface hardness and scratch resistance, and 4 or more ( A (meth) acrylate having a (meth) acryloyl group is more preferable, and a (meth) acrylate having 6 or more (meth) acryloyl groups in one molecule is more preferable. As said component (A), these 1 type, or 2 or more types of mixtures can be used.

(B) Water repellent:
The component (B) functions to increase slipperiness, dirt adhesion prevention, and dirt wiping.

Examples of the water repellent include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax; silicon-based water repellents such as silicon oil, silicon resin, polydimethylsiloxane, and alkylalkoxysilane. Agents; fluorine-containing water repellents such as fluoropolyether water repellents and fluoropolyalkyl water repellents; and the like. As said component (B), these 1 type, or 2 or more types of mixtures can be used.

Among these, as the component (B), a fluoropolyether water repellent is preferable from the viewpoint of water repellent performance. From the viewpoint of preventing troubles such as a chemical bond or strong interaction between the component (A) and the component (B) and bleeding out of the component (B), the component (B) includes A water repellent containing a compound containing a (meth) acryloyl group and a fluoropolyether group (hereinafter abbreviated as a (meth) acryloyl group-containing fluoropolyether water repellent) is more preferable. More preferable as the component (B) is to appropriately adjust the chemical bond or interaction between the component (A) and the component (B), from the viewpoint of expressing good water repellency while maintaining high transparency. It is a mixture of an acryloyl group-containing fluoropolyether water repellent and a methacryloyl group-containing fluoropolyether water repellent.

The (meth) acryloyl group-containing fluoropolyether water repellent is clearly distinguished from the component (A) in that it contains a fluoropolyether group in the molecule. In the present specification, the compound having a fluoropolyether group and having a (meth) acryloyl group is a (meth) acryloyl group-containing fluoropolyether water repellent and is the component (B).

The amount of the component (B) is usually 7 parts by mass or less, preferably 4 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of preventing troubles such as bleeding out of the component (B). Or less, more preferably 2 parts by mass or less. On the other hand, from the viewpoint of obtaining the effect of using the component (B), it may be usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more.

(C) Silane coupling agent:
The component (C) serves to improve the adhesion between the first hard coat and the second hard coat.

Silane coupling agents include hydrolyzable groups (for example, alkoxy groups such as methoxy group and ethoxy group; acyloxy groups such as acetoxy group; halogen groups such as chloro group; and the like) and organic functional groups (for example, amino groups, A silane compound having at least two different reactive groups such as a mercapto group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group. Among these, as the component (C), from the viewpoint of adhesion, a silane coupling agent having an amino group (a silane compound having an amino group and a hydrolyzable group) and a silane coupling agent having a mercapto group ( A silane compound having a mercapto group and a hydrolyzable group is preferred. From the viewpoint of adhesion and odor, a silane coupling agent having an amino group is more preferable.

Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2. -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, Examples thereof include N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and the like.

Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

As said component (C), these 1 type, or 2 or more types of mixtures can be used.

The compounding amount of the component (C) is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, from the viewpoint of surely obtaining an adhesion improving effect with respect to 100 parts by mass of the component (A). More preferably, it may be 0.1 parts by mass or more. On the other hand, from the viewpoint of the pot life of the paint, it may be usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 part by mass or less.

From the viewpoint of improving the curability by active energy rays, the first hard coat-forming coating material has a compound having two or more isocyanate groups (—N═C═O) in one molecule and / or photopolymerization. It is preferable to further include an initiator.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, and a trimethylolpropane adduct of isophorone diisocyanate. Polyisocyanates such as methylolpropane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and block isocyanates of the above polyisocyanates A urethane cross-linking agent can be used. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. it can. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

The first hard coat-forming coating material includes, as desired, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain-preventing agent, a printability improving agent, an antioxidant, a weathering stabilizer, One or more additives such as a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, organic fine particles, and an organic colorant can be contained.

The first hard coat-forming coating material may contain a solvent as desired in order to dilute to a concentration that facilitates coating. The solvent is not particularly limited as long as it does not react with the above components (A) to (C) and other optional components or catalyze (promote) the self-reaction (including degradation reaction) of these components. Not. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As said solvent, these 1 type, or 2 or more types of mixtures can be used.

The said 1st hard-coat formation coating material can be obtained by mixing and stirring these components.

The method for forming the first hard coat using the first hard coat forming paint is not particularly limited, and a known web coating method can be used. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

The thickness of the first hard coat is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoints of impact resistance to falling balls, scratch resistance and hardness. On the other hand, from the viewpoint of hardness and adhesion to the second hard coat, the thickness may be preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less.

Second hard coat In one aspect, the second hard coat forming paint is not limited except that it contains inorganic particles, and any paint can be used. Preferred examples of the second hard coat-forming coating material further include a coating material that contains an active energy ray-curable resin and that can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. be able to.

The active energy ray-curable resin is described above in the description of the first hard coat forming coating material. As said active energy ray curable resin, these 1 type, or 2 or more types of mixtures can be used.

When the hard coat laminated film of the present invention is used as a display face plate of an image display device having a touch panel function, particularly as a display face plate of a smartphone or tablet terminal, the falling ball impact resistance, surface hardness, transparency, scratch resistance, scratch resistance, From the viewpoints of bendability, color tone, surface appearance, interlayer adhesion strength, and machinability, the second hard coat-forming coating material is (d1) a polysiloxane having three or more (meth) acryloyl groups in one molecule. A paint containing a functional (meth) acrylate; (d2) a compound having two or more secondary thiol groups in one molecule; and (E) inorganic fine particles having an average particle diameter of 1 to 300 nm is preferable.

The coating material for forming the second hard coat includes (d1) a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule; (d2) two or more secondary thiols in one molecule. (D3) (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth) Also preferred is a paint comprising 1) one or more (meth) acrylates selected from the group consisting of acrylates; and (E) inorganic fine particles having an average particle size of 1 to 300 nm.

The paint for forming the second hard coat includes (D) 100 parts by mass of a polymerizable compound; and (E) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm. (D1) Polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule 60 to 30% by mass; (d2) Two or more secondary thiol groups in one molecule And (d3) (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule And a coating material consisting of 0 to 50% by mass of one or more (meth) acrylates selected from the group consisting of urethane (meth) acrylates. Here, the sum of the component (d1), the component (d2), and the component (d3) is 100% by mass;

(D1) Polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule:
The component (d1) is a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule. The component (d1) functions to increase the surface hardness.

Examples of the component (d1) include (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; (Meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth) acryloyl such as tripentaerythritol acrylate Examples thereof include a group-containing octafunctional reactive monomer and a polymer (oligomer or prepolymer) having one or more of these as constituent monomers. As said component (d1), these 1 type, or 2 or more types of mixtures can be used. In the present specification, (meth) acrylate means acrylate or methacrylate.

(D2) Compound having two or more secondary thiol groups in one molecule:
The component (d2) is a compound having two or more secondary thiol groups in one molecule. The component (d2) functions to improve the falling ball impact resistance. The component (d2) functions to drastically improve the falling ball impact resistance by interacting with the component (d3).

In the present specification, the compound having two or more secondary thiol groups in one molecule and having a (meth) acryloyl group is the component (d2).

The component (d2) has one or more (meth) acryloyl groups, vinyl groups, epoxy groups, and isocyanate functional groups other than secondary thiol groups in one molecule. However, those having no polymerizable functional group are preferred from the viewpoint of impact resistance to falling balls.

Examples of the compound having two or more secondary thiol groups in one molecule include 1,4-bis (3-mercaptobutyryloxy) butane and 1,3,5-tris (3-mercaptobutyryloxy). Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), And pentaerythritol tetrakis (3-mercaptobutyrate). Among these, a compound having 2 or 3 secondary thiol groups in one molecule is preferable from the viewpoint of impact resistance to falling balls. As said component (d2), these 1 type, or 2 or more types of mixtures can be used.

(D3) (Meth) acrylate having two (meth) acryloyl groups in one molecule:
The component (d3) includes (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth). One or more (meth) acrylates selected from the group consisting of acrylates. The component (d3) preferably contains an aliphatic urethane (meth) acrylate having two (meth) acryloyl groups. The component (d3) serves to improve the falling ball impact resistance. The component (d3) functions to dramatically improve the falling ball impact resistance by interacting with the component (d2). In the present specification, urethane (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule is the component (d3).

Examples of the (meth) acrylate having one or two (meth) acryloyl groups in one molecule include polyester (meth) acrylate, polyacryl (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and epoxy. Examples thereof include prepolymers or oligomers such as (meth) acrylates and polyether (meth) acrylates having one or two (meth) acryloyl groups in one molecule.

Examples of the (meth) acrylate having two (meth) acryloyl groups in one molecule include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, and 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) Propane can be raised.

The (meth) acrylate having two (meth) acryloyl groups in one molecule is not particularly limited, but may typically be a compound having a structure represented by the following general formula (1). . In the formula, R ₁ and R ₂ are each independently H (hydrogen atom) or CH ₃ (methyl group). R ₃ is an alkyl branch, a cyclic hydrocarbon group, an ether group, or an aliphatic alkylene group which may have a hydroxyl group. R ₃ may typically be “(CH ₂ ) n”. Here, n may be a natural number of usually 2 or more, preferably 4 to 20, more preferably 6 to 12. R3 may preferably contain a bridged ring hydrocarbon group. Examples of the bridged ring hydrocarbon include bicyclo [2.1.0] pentane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, and bicyclo [2.2.1] hepta. -2-ene, bicyclo [3.2.1] octane, tricyclo [3.2.1.0 ^2,7 ] octane, adamantane and the like can be mentioned.

Although it does not specifically limit as said (meth) acrylate which has two (meth) acryloyl groups in the said molecule | numerator, More preferably, you may be tricyclodecane dimethanol di (meth) acrylate. Surprisingly, by including this in the second hard coat forming paint, the second hard coat is not a layer forming the surface of the hard coat laminated film, but it is scratch resistant, particularly steel wool resistant. The characteristics are greatly improved. Example 14 of the following example is an example using tricyclodecane dimethanol diacrylate, but the hard coat laminated film is placed on the Gakushin Tester of JIS L0849: 2013 so that the first hard coat becomes the surface. Then, after attaching # 0000 steel wool to the friction terminal of the Gakushin type testing machine, load 500g, and reciprocate the surface of the test piece under the conditions of a friction terminal moving speed of 300mm / min and moving distance of 30mm. After rubbing 500 times, when the rubbing part was visually observed, no scratch was observed.

The tricyclodecane dimethanol di (meth) acrylate is a compound having a structure represented by the following general formula (2). In the formula, R ₁ and R ₂ are each independently H (hydrogen atom) or CH ₃ (methyl group).

Examples of the (meth) acrylate having one (meth) acryloyl group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenyl cellosolve (meth) Acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) Acrylate, trifluoroethyl (meth) acrylate, and, and the like trimethylsiloxy ethyl methacrylate.

Examples of the (meth) acrylate having one (meth) acryloyl group in one molecule include (meth) acrylic acid adducts of esters or ester derivatives, N-substituted (meth) acrylamide compounds, and the like. it can.

Although it does not specifically limit as said (meth) acrylic acid adduct of ester or ester derivative, Typically, it may be a compound which has a structure represented by following General formula (3). In the formula, R ₁ represents a hydrogen atom or a methyl group. R _{2 and} R ₃ are each independently an alkyl branch, a cyclic hydrocarbon group, an ether group, or an aliphatic alkylene group which may have a hydroxyl group. R _{2 and} R ₃ may each independently be typically “(CH ₂ ) n”. Here, n may be a natural number of usually 1 or more, preferably 1 to 20, more preferably 2 to 12. R ₄ is a hydrogen atom or an alkyl branch, a cyclic hydrocarbon group, an ether group, or an aliphatic alkyl group which may have a hydroxyl group.

Examples of the (meth) acrylic acid adduct of the ester or ester derivative include 2- (meth) acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-acryloyloxyethyl- Examples include 2-hydroxyethyl-phthalic acid.

Although it does not specifically limit as said N-substituted (meth) acrylamide compound, Typically, it may be a compound which has a structure represented by following General formula (4). In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₃ represents an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group or an amino group, or R ₂ and R ₃ are Together, they form a 5-membered or 6-membered ring which may have an oxygen atom as a ring member together with the nitrogen atom to which they are bonded. The “N-substituted (meth) acrylamide compound” means an N-substituted acrylamide compound or an N-substituted methacrylamide compound.

Examples of the N-substituted (meth) acrylamide compound include N-methyl (meth) acrylamide, N-methylol (meth) acrylamide butyl ether, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N -Isopropyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide N, N-diethyl (meth) acrylamide, N-methyl, N-ethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide methyl ether, N-methylo Ru (meth) acrylamide ethyl ether, N-methylol (meth) acrylamide propyl ether, N-butoxymethyl (meth) acrylamide, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, (meth) acryloylmorpholine, etc. Can give.

The urethane (meth) acrylate is a compound having a urethane structure (—NH—CO—O—) or a derivative thereof having one or more (meth) acryloyl groups. In the present specification, urethane (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule is the component (d3).

The urethane (meth) acrylate is not particularly limited, but typically, a compound having two or more isocyanate groups (—N═C═O) in one molecule, a polyol compound, and a hydroxyl group-containing (meth) acrylate. In other words, it may contain a structural unit derived from these compounds.

Examples of the compound having two or more isocyanate groups in one molecule include two compounds in one molecule such as diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and methylene bis (4-cyclohexyl isocyanate). The compound which has an isocyanate group can be mention | raise | lifted.

Examples of the compound having two or more isocyanate groups in one molecule include, for example, a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, a trimethylolpropane adduct of isophorone diisocyanate, and tolylene Examples thereof include polyisocyanates such as isocyanurate of isocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, and biuret of hexamethylene diisocyanate.

As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used.

Examples of the polyol compound include polyether polyol, polyester polyol, and polycarbonate polyol.

Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyalkylene oxides such as polyethylene oxide and polypropylene oxide; copolymers of ethylene oxide and propylene oxide; ethylene A copolymer of an oxide and tetrahydrofuran; a copolymer of a dihydric phenol compound and a polyoxyalkylene glycol; and a dihydric phenol and an alkylene oxide having 2 to 4 carbon atoms (for example, ethylene oxide, propylene oxide, 1,2- Butylene oxide, 1,4-butylene oxide, etc.) and a copolymer with one or more thereof.

Examples of the polyester polyol include poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelate), poly (butylene sebacate), and Examples include polycaprolactone.

Examples of the polycarbonate polyol include poly (butanediol carbonate), poly (hexanediol carbonate), and poly (nonanediol carbonate).

As said polyol compound, these 1 type, or 2 or more types of mixtures can be used.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylate, and 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate; dipropylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, And glycol-based (meth) acrylates such as polypropylene glycol mono (meth) acrylate; glycerin-based (meth) acrylates such as glycerin di (meth) acrylate; fatty acid-modified glycidyl Glycidyl-based (meth) acrylates such as (meth) acrylate; phosphorus-containing (meth) acrylates such as 2-hydroxyethylacryloyl phosphate; esters or ester derivatives such as 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate (Meth) acrylic acid adducts such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, and ethylene oxide modified dipentaerythritol penta (meth) acrylate Pentaerythritol (meth) acrylate; and caprolactone-modified 2-hydroxyethyl (meth) acrylate, caprolactone-modified pentaerythritol tri Meth) acrylate, and caprolactone-modified (meth) acrylates such as caprolactone-modified dipentaerythritol penta (meth) acrylate; and the like.

As said hydroxyl-containing (meth) acrylate, these 1 type, or 2 or more types of mixtures can be used.

The (meth) acryloyl group possessed by the urethane (meth) acrylate is usually 12 or less, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, most preferably from the viewpoint of falling ball impact resistance. There may be two. On the other hand, from the viewpoint of scratch resistance, it may usually be 2 or more. In one embodiment, the urethane (meth) acrylate includes an aliphatic urethane (meth) acrylate having two (meth) acryloyl groups in one molecule.

As the component (d3), (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth) ) A mixture of one or more (meth) acrylates selected from the group consisting of acrylates can be used.

The proportion of the component (d1) in the polymerizable compound (D) is usually 60% by mass or less, preferably 55% by mass or less, from the viewpoint of falling ball impact resistance. On the other hand, from the viewpoint of surface hardness, it may be usually 30% by mass or more, preferably 40% by mass or more. The proportion of the component (d2) in the polymerizable compound (D) is usually 5% by mass or more, preferably 20% by mass or more from the viewpoint of falling ball impact resistance. On the other hand, from the viewpoint of surface hardness, it may be usually 70% by mass or less, preferably 50% by mass or less. The proportion of the component (d3) in the polymerizable compound (D) is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably from the viewpoint of impact resistance to falling balls. It may be 15% by mass or more. On the other hand, from the viewpoint of surface hardness, it may be usually 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less. Here, the sum of the component (d1), the component (d2), and the component (d3) is 100% by mass;

(E) Inorganic fine particles having an average particle diameter of 1 to 300 nm:
The component (E) functions to dramatically increase the surface hardness of the hard coat laminated film of the present invention.

Examples of the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Examples thereof include metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal sulfide fine particles; metal nitride fine particles; and metal fine particles.

Among these, in order to obtain a hard coat having higher surface hardness, fine particles of silica or aluminum oxide are preferable, and fine particles of silica are more preferable. Examples of commercially available silica fine particles include Snowtex (trade name) manufactured by Nissan Chemical Industries, Ltd., Quartron (trade name) manufactured by Fuso Chemical Industries, Ltd., and the like.

For the purpose of increasing the dispersibility of the inorganic fine particles in the paint or increasing the surface hardness of the obtained hard coat, the surface of the inorganic fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent. An aluminate coupling agent; an organic compound having a reactive functional group such as an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group; and an epoxy group; and a fatty acid, a fatty acid metal salt, etc. It is preferable to use a material treated with a surface treatment agent or the like.

As said component (E), these 1 type, or 2 or more types of mixtures can be used.

The average particle size of the component (E) is usually 300 nm or less, preferably 200 nm or less, more preferably 120 nm or less, from the viewpoint of reliably obtaining the effect of improving the hardness of the hard coat. On the other hand, there is no particular lower limit on the average particle diameter, but normally available inorganic fine particles are fine at most about 1 nm.

In this specification, the average particle size of the inorganic fine particles is the particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. It is the particle diameter at which the accumulation is 50% by mass.

The compounding amount of the component (E) is usually 50 parts by mass or more, preferably 80 parts by mass or more, more preferably 100 parts by mass or more, from the viewpoint of surface hardness, with respect to 100 parts by mass of the component (D). Preferably it may be 150 parts by mass or more. On the other hand, from the viewpoint of transparency, it may be usually 300 parts by mass or less, preferably 240 parts by mass or less.

(F) Leveling agent:
From the viewpoint of making the surface of the second hard coat excellent (smooth) and facilitating the formation of the first hard coat, the second hard coat forming paint further includes (F) a leveling agent. Is preferred.

Examples of the leveling agent include acrylic leveling agents, silicon leveling agents, fluorine leveling agents, silicon / acrylic copolymer leveling agents, fluorine-modified acrylic leveling agents, fluorine-modified silicon leveling agents, and functionalities thereof. Leveling agents and the like into which groups (for example, alkoxy groups such as methoxy group and ethoxy group, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, and isocyanate groups) are introduced. Can do. Among these, the component (F) is preferably a silicon / acrylic copolymer leveling agent. As said component (F), these 1 type, or 2 or more types of mixtures can be used.

The amount of the component (F) is usually 0 from the viewpoint of improving the surface of the second hard coat and facilitating the formation of the first hard coat with respect to 100 parts by mass of the component (D). 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more. On the other hand, from the viewpoint of allowing the first hard coat-forming coating material to be satisfactorily applied without being repelled on the second hard coat, it is usually 1 part by mass or less, preferably 0.6 parts by mass or less, More preferably, it may be 0.4 parts by mass or less.

From the viewpoint of improving the curability by active energy rays, the second hard coat-forming coating material has a compound having two or more isocyanate groups (—N═C═O) in one molecule and / or photopolymerization. It is preferable to further include an initiator.

The compound having two or more isocyanate groups in one molecule is described above in the description of the first hard coat forming coating material. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used.

The photopolymerization initiator is described above in the description of the first hard coat forming coating material. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

For the second hard coat forming coating, an antistatic agent, a surfactant, a thixotropic agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, and a light resistance stability are optionally added. One or more additives such as an agent, an ultraviolet absorber, a heat stabilizer, a colorant, and organic fine particles can be contained.

The second hard coat-forming coating material may contain a solvent as desired in order to dilute to a concentration that facilitates coating. If the said solvent does not react with the said component (D), the said component (E), and other arbitrary components, or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components, There is no particular limitation. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. Of these, 1-methoxy-2-propanol is preferred. As said solvent, these 1 type, or 2 or more types of mixtures can be used.

The second hard coat-forming coating material can be obtained by mixing and stirring these components.

The method for forming the second hard coat using the second hard coat forming paint is not particularly limited, and a known web coating method can be used. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, dip coating, spray coating, spin coating, air knife coating, and die coating.

From the viewpoint of surface hardness, the thickness of the second hard coat is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and further preferably 18 μm or more. On the other hand, from the viewpoint of suppressing warpage, it may be preferably 30 μm or less, more preferably 27 μm or less, and even more preferably 25 μm or less.

Transparent resin film:
The said transparent resin film is a layer used as the transparent film base material for forming the said 1st hard coat and the said 2nd hard coat on it. The transparent resin film is not limited except that it has high transparency and is not colored, and any transparent resin film can be used. Examples of the transparent resin film include cellulose ester resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymers; polymethyl methacrylate, polyethyl methacrylate, And acrylic resins such as vinylcyclohexane- (meth) acrylate methyl copolymer; aromatic polycarbonate resins; polyolefin resins such as polypropylene and 4-methyl-pentene-1; polyamide resins; polyarylate resins; Examples thereof include a polymer type urethane acrylate resin; and a polyimide resin. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, these films include the laminated | multilayer film which laminated | stacked these 1 type (s) or 2 or more types two or more layers.

The thickness of the transparent resin film is not particularly limited, and can be any thickness as desired. From the viewpoint of handleability of the hard coat laminated film of the present invention, it may be usually 20 μm or more, preferably 50 μm or more. When the hard coat laminated film of the present invention is used for an application that does not require high rigidity, it may be usually 250 μm or less, preferably 150 μm or less from the viewpoint of economy. When the hard coat laminated film of the present invention is used as a display face plate, it may be usually 300 μm or more, preferably 500 μm or more, more preferably 600 μm or more from the viewpoint of maintaining rigidity. Further, from the viewpoint of meeting the demand for thinning the apparatus, it may be usually 1500 μm or less, preferably 1200 μm or less, more preferably 1000 μm or less.

The transparent resin film is preferably an acrylic resin transparent resin film.

As the acrylic resin, for example, (meth) acrylic acid ester (co) polymer, structural units derived from (meth) acrylic acid ester are mainly (usually 50 mol% or more, preferably 65 mol% or more, more preferably And the like, and copolymers thereof, and modified products thereof. In addition, (meth) acryl means acryl or methacryl. The (co) polymer means a polymer or a copolymer.

Examples of the (meth) acrylate ester (co) polymer include poly (meth) acrylate methyl, poly (meth) acrylate ethyl, poly (meth) acrylate propyl, poly (meth) acrylate butyl, ( Examples thereof include a methyl (meth) acrylate / butyl (meth) acrylate copolymer and an ethyl (meth) acrylate / butyl (meth) acrylate copolymer.

Examples of the copolymer mainly containing a structural unit derived from the above (meth) acrylic acid ester include, for example, ethylene / methyl (meth) acrylate copolymer, styrene / methyl (meth) acrylate copolymer, vinylcyclohexane / Examples thereof include (meth) methyl acrylate copolymer, maleic anhydride / (meth) methyl acrylate copolymer, and N-substituted maleimide / (meth) methyl acrylate copolymer.

Examples of the modified substance include a polymer in which a lactone ring structure is introduced by an intramolecular cyclization reaction; a polymer in which glutaric anhydride is introduced by an intramolecular cyclization reaction; and an imidizing agent (for example, methyl Amine, cyclohexylamine, ammonia, etc.) and a polymer in which an imide structure has been introduced by reaction (hereinafter sometimes referred to as a poly (meth) acrylimide resin). Can do.

Examples of the transparent resin film of the acrylic resin include films of one kind or a mixture of two or more kinds thereof. Moreover, these films include the laminated | multilayer film which laminated | stacked these 1 type (s) or 2 or more types two or more layers.

The transparent resin film is more preferably a vinylcyclohexane · (meth) methyl acrylate copolymer film. It becomes a hard coat laminated film excellent in falling ball impact resistance, surface hardness, scratch resistance, transparency, surface smoothness, appearance, rigidity, and moisture resistance, and can be suitably used as a display face plate for smartphones and tablet terminals. The content of the structural unit derived from methyl (meth) acrylate in the vinylcyclohexane- (meth) acrylic acid methyl copolymer is usually 50%, assuming that the sum of the structural units derived from all polymerizable monomers is 100 mol%. It may be -95 mol%, preferably 65-90 mol%, more preferably 70-85 mol%. Here, “polymerizable monomer” means methyl (meth) acrylate, vinylcyclohexane, and a monomer copolymerizable therewith. The copolymerizable monomer is usually a compound having a carbon / carbon double bond, and typically a compound having an ethylenic double bond.

The transparent resin film is more preferably a poly (meth) acrylimide resin film. It becomes a hard coat laminated film with excellent impact resistance to falling balls, surface hardness, scratch resistance, transparency, surface smoothness, appearance, rigidity, heat resistance, and dimensional stability. It can be suitably used as a conductive substrate.

The yellowness index of the acrylic resin (measured using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation according to JIS K 7105: 1981) is preferably 3 or less, more preferably 2. Hereinafter, it may be 1 or less. By using an acrylic resin having a yellowness index of 3 or less, a hard coat laminated film that can be suitably used as a member of an image display device can be obtained. The lower the yellowness index, the better.

The melt mass flow rate of the acrylic resin (measured in accordance with ISO 1133 under the conditions of 260 ° C. and 98.07 N) is preferably 0.1 to 20 g / 10 minutes from the viewpoint of extrusion load and melt film stability. Preferably, it may be 0.5 to 10 g / 10 minutes.

The acrylic resin can contain a core shell rubber, if desired. When the acrylic resin is 100 parts by mass, the core shell rubber is usually used in an amount of 0 to 100 parts by mass, preferably 3 to 50 parts by mass, more preferably 5 to 30 parts by mass. Impact resistance can be increased.

Examples of the core shell rubber include methacrylic ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Examples thereof include core-shell rubbers such as an acid ester graft copolymer, a methacrylic ester / acrylic ester rubber graft copolymer, and a methacrylic ester / acrylonitrile / acrylic ester rubber graft copolymer. As said core shell rubber, these 1 type, or 2 or more types of mixtures can be used.

In addition, the acrylic resin may include a thermoplastic resin other than the acrylic resin and the core-shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; a lubricant, an antioxidant, An additive such as a weather resistance stabilizer, a heat stabilizer, a release agent, an antistatic agent, and a surfactant may be further included. The amount of these optional components is usually about 0.01 to 10 parts by mass when the acrylic resin is 100 parts by mass.

The transparent resin film is more preferably a transparent multilayer in which a first acrylic resin layer (α1); an aromatic polycarbonate resin layer (β); and a second acrylic resin layer (α2) are directly laminated in this order. It is a film. In the present specification, the present invention will be described on the assumption that the touch surface is formed on the α1 layer side.

Acrylic resins are excellent in surface hardness, but cutting processability tends to be insufficient, whereas aromatic polycarbonate resins are excellent in cutting processability, but surface hardness tends to be insufficient. . Therefore, by using the transparent multilayer film having the above-mentioned layer structure, it is possible to easily obtain a hard coat laminated film that compensates for both weak points and is excellent in both surface hardness and cutting workability.

The layer thickness of the α1 layer is not particularly limited, but is usually 20 μm or more, preferably 40 μm or more, more preferably 60 μm or more, and still more preferably 80 μm or more, from the viewpoint of the surface hardness of the hard coat laminated film of the present invention. Good.

The layer thickness of the α2 layer is not particularly limited, but is preferably the same layer thickness as the α1 layer from the viewpoint of curl resistance of the hard coat laminated film of the present invention.

Here, the “same layer thickness” should not be interpreted as the same layer thickness in a physicochemically strict sense. It should be construed that the layer thickness is the same within the range of process and quality control that is usually performed industrially. This is because the curl resistance of the multilayer film can be kept good if the layer thickness is the same within the range of the amplitude of process and quality control that is usually performed industrially. In the case of an unstretched multilayer film by the T-die coextrusion method, for example, when the set layer thickness is 70 μm, the process / quality control is usually performed with a width of about −5 to +5 μm. 75 μm should be interpreted as the same.

The layer thickness of the β layer is not particularly limited, but may be usually 20 μm or more, preferably 80 μm or more, from the viewpoint of the machinability of the hard coat laminated film of the present invention.

The acrylic resin used for the α1 layer and the α2 layer has been described above.

The acrylic resin used for the α1 layer and the acrylic resin used for the α2 layer may have different resin characteristics, for example, different acrylic resins such as types, melt mass flow rates, and glass transition temperatures. However, from the viewpoint of curling resistance of the hard coat laminated film of the present invention, it is preferable to use those having the same resin characteristics. For example, using the same lot of the same grade is one preferred embodiment.

Examples of the aromatic polycarbonate resin used for the β layer include aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and phosgene. A polymer obtained by an interfacial polymerization method with an aromatic dihydroxy compound such as bisphenol A, dimethyl bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and carbonic acid such as diphenyl carbonate. One or a mixture of two or more aromatic polycarbonate resins such as a polymer obtained by a transesterification reaction with a diester can be used.

As a preferable optional component that can be included in the aromatic polycarbonate-based resin, a core-shell rubber can be exemplified. When the total of the aromatic polycarbonate-based resin and the core-shell rubber is 100 parts by mass, the core-shell rubber is 0-30 parts by mass (aromatic polycarbonate-based resin 100-70 parts by mass), preferably 0-10 parts by mass (aromatic By using it in an amount of 100 to 90 parts by mass of a polycarbonate-based resin, cutting workability and impact resistance can be further improved.

Examples of the core shell rubber include methacrylic ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Examples thereof include core-shell rubbers such as an acid ester graft copolymer, a methacrylic ester / acrylic ester rubber graft copolymer, and a methacrylic ester / acrylonitrile / acrylic ester rubber graft copolymer. As said core shell rubber, these 1 type, or 2 or more types of mixtures can be used.

The aromatic polycarbonate-based resin may be a thermoplastic resin other than the aromatic polycarbonate-based resin and the core-shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; An additive such as an antioxidant, a weather resistance stabilizer, a heat stabilizer, a mold release agent, an antistatic agent, and a surfactant may be further included. The compounding amount of these optional components is usually about 0.01 to 10 parts by mass when the total of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass.

The method for producing the transparent resin film is not particularly limited. As a preferable production method when the transparent resin film is a poly (meth) acrylimide resin film, the method described in JP-A-2015-033844 can be exemplified. In the case where the transparent resin film is a transparent multilayer film in which the first acrylic resin layer (α1); the aromatic polycarbonate resin layer (β); the second acrylic resin layer (α2) are directly laminated in this order. As a preferable production method, the method described in JP-A-2015-083370 can be exemplified. In forming the hard coat, easy adhesion treatment such as corona discharge treatment or anchor coat formation may be performed in advance on the hard coat formation surface or both surfaces of the transparent resin film in order to increase the adhesive strength with the hard coat. .

The hard coat laminated film of the present invention preferably has the first hard coat, the second hard coat, the layer of the transparent resin film, and the third hard coat in order from the surface side. By forming the third hard coat, both the force to curl the hard coat laminated film to one side (hereinafter sometimes abbreviated as curl force) and the force to curl to the other work both. become. The occurrence of curling can be suppressed by canceling these two curling forces to zero.

In recent years, for the purpose of reducing the weight of an image display device, a two-layer touch panel (so-called one glass solution) in which a touch sensor is directly formed on the back side of a display face plate has been proposed. In order to further reduce the weight, a one plastic solution that replaces the so-called one glass solution has been proposed. When the hard coat laminated film of the present invention is used for a one plastic solution that replaces the so-called one glass solution, the above-mentioned third hard coat is formed to give suitable characteristics as a printing surface. Becomes easier.

The hard coat laminated film of this invention may have arbitrary layers other than the said 1st hard coat, the said 2nd hard coat, the layer of the said transparent resin film, and the said 3rd hard coat as needed. Examples of the optional layer include a hard coat other than the first to third hard coats, an anchor coat, an adhesive layer, a transparent conductive layer, a high refractive index layer, a low refractive index layer, and an antireflection functional layer. be able to.

FIG. 1 is a conceptual cross-sectional view showing an example of the hard coat laminated film of the present invention. In order from the touch surface side, first hard coat 1, second hard coat 2, first poly (meth) acrylimide resin layer (α1) 3, aromatic polycarbonate resin layer (β) 4, second poly (meta) ) An acrylic imide resin layer (α2) 5 and a third hard coat 6 are provided.

The hard coat laminated film of this invention bonds the surface on the opposite side to the said 1st hard coat surface, and float plate glass, and freely attaches the steel ball of mass 110g to the said 1st hard coat surface from 30cm in height. When it is dropped and visually observed from the first hard coat surface side, it is preferable that no trace of striking with a steel ball is recognized. The height measured according to the test (a) of the following examples of the hard coat laminated film of the present invention is more preferably 40 cm or more, still more preferably 50 cm or more, still more preferably 60 cm or more, still more preferably 70 cm or more, Most preferably, it is 80 cm or more. The height is preferably higher. By satisfying the above criteria, a smartphone or tablet terminal in which the hard coat laminated film of the present invention is used as a display face plate can be expected not to be broken even if it is accidentally dropped during use.

The hard coat laminated film of the present invention uses the pencil “Uni (trade name)” of Mitsubishi Pencil Co., Ltd. according to JIS K 5600-5-4: 1999 except that the load is 1 kg. The pencil hardness measured for is preferably 3H or higher, more preferably 4H or higher, and even more preferably 5H or higher. A higher pencil hardness is preferred. The hard coat laminated film of the present invention can be suitably used as a display face plate.

In the hard coat laminated film of the present invention, the water contact angle on the surface of the first hard coat is preferably 100 degrees or more, more preferably 105 degrees or more. When the hard coat laminated film of the present invention is used as a display face plate of a touch panel, the first hard coat usually forms a touch surface. When the water contact angle on the surface of the first hard coat is 100 degrees or more, the touch panel can be operated by sliding a finger or a pen as desired on the touch surface. From the viewpoint of sliding a finger or pen as desired, a higher water contact angle is preferable, and there is no particular upper limit for the water contact angle, but from the viewpoint of slipperiness, about 120 degrees is usually sufficient. Here, the water contact angle is a value measured according to the test (c) of the following example.

The hard coat laminated film of the present invention may preferably have a water contact angle of 100 degrees or more after 20,000 cotton swabs on the surface of the first hard coat. More preferably, the water contact angle after 25,000 cotton swabs may be 100 degrees or more. When the water contact angle after 20,000 cotton reciprocations is 100 degrees or more, it is possible to maintain surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like. The larger the number of cotton wipes that can maintain a water contact angle of 100 degrees or more, the better. Here, the water contact angle after cotton wiping is a value measured according to the test (d) of the following examples.

The hard coat laminated film of the present invention preferably has a total light transmittance (measured according to JIS K 7361-1: 1997, using a turbidimeter “NDH2000 (trade name)” manufactured by Nippon Denshoku Industries Co., Ltd.). % Or more, more preferably 88% or more, still more preferably 90% or more. When the total light transmittance is 85% or more, the hard coat laminated film of the present invention can be suitably used as an image display device member. A higher total light transmittance is preferable.

The yellowness index of the hard coat laminated film of the present invention (measured using a color meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation in accordance with JIS K 7105: 1981) is preferably 3 or less. Preferably it may be 2 or less, more preferably 1 or less. When the yellowness index is 3 or less, the hard coat laminated film of the present invention can be suitably used as an image display device member. The lower the yellowness index, the better.

The hard coat laminated film of the present invention may have a minimum bending radius of preferably 40 mm or less, more preferably 35 mm or less, and even more preferably 30 mm or less. When the minimum bending radius is preferably 40 mm or less, the hard coat laminated film of the present invention can be easily handled as a film roll, which is advantageous in terms of production efficiency. The smaller the minimum bending radius, the better. Here, the minimum bending radius is a value measured according to the test (h) of the following example.

The minimum bend radius is a bend radius immediately before a crack is generated on the surface of the bent portion when the hard coat laminated film is bent, and is an index indicating the limit of bending. The bending radius is defined in the same way as the curvature radius.

The radius of curvature is defined as follows. The length from the M point to the N point of the curve is ΔS; the difference between the slope of the tangent at the M point and the slope of the tangent at the N point is Δα; a straight line perpendicular to the tangent at the M point and intersecting at the M point When the intersection point with a straight line that is perpendicular to the tangent line at the N point and intersects at the N point is O; and when ΔS is sufficiently small, the curve from the M point to the N point can be approximated to an arc. (FIG. 2). The radius at this time is defined as the radius of curvature. When the radius of curvature is R, ∠MON = Δα, and when ΔS is sufficiently small, Δα is also sufficiently small, so ΔS = RΔα is established, and R = ΔS / Δα.

Production method:
The manufacturing method in particular of the hard coat laminated film of this invention is not restrict | limited, It can manufacture by arbitrary methods. As a preferable manufacturing method, from the viewpoint of adhesion between the first hard coat and the second hard coat, for example, (1) a wet coating made of the second hard coat forming paint is applied on the transparent resin film. Forming a film;
(2) The wet coating film made of the second hard coat forming paint has an active energy ray with an integrated light amount of 1 to 230 mJ / cm ² , preferably 5 to 200 mJ / cm ² , more preferably 10 to 160 mJ / cm. ² , more preferably 20 to 120 mJ / cm ² , most preferably 30 to 100 mJ / cm ^2, and the wet coating film made of the second hard coat forming paint is applied in a dry-to-touch state. Forming a film;
(3) forming a wet paint film made of the first hard coat forming paint on the touch-dried paint film made of the second hard coat forming paint; and (4) the first The wet coating film comprising a hard coat forming coating is preheated to a temperature of 30 to 100 ° C., preferably 40 to 85 ° C., more preferably 50 to 75 ° C., and the active energy ray is integrated to 240 to 10,000 mJ / cm. ² , preferably 320 to 5000 mJ / cm ² , more preferably 360 to 2000 mJ / cm ² .

In the step (1), the method for forming the wet coating film composed of the second hard coat forming coating is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The wet coating film made of the second hard coat forming paint formed in the step (1) becomes dry to the touch or has no tackiness in the step (2) and directly touches the web device. However, handling problems such as sticking will no longer occur. Therefore, in the next step (3), a wet paint film made of the first hard coat forming paint is formed on the touch-dried paint film made of the second hard coat forming paint. Will be able to.

In this specification, “the coating film is in a dry-to-touch state (without tackiness)” means that there is no problem in handling even when the coating film directly touches the web device. .

Irradiation with active energy rays in the step (2) depends on the characteristics of the paint used as the second hard coat-forming paint, but from the viewpoint of ensuring that the paint film is dry to the touch, the integrated light quantity is usually 1 mJ. / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, more preferably 20 mJ / cm ² or more, and most preferably carried out such that 30 mJ / cm ² or more. On the other hand, from the viewpoint of adhesion between the first hard coating and second hard coating, integrated light quantity usually 230 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably 160 mJ / cm ² or less, more preferably 120mJ / Cm ² or less, most preferably 100 mJ / cm ² or less.

In the step (2), it is preferable to pre-dry the wet coating film made of the second hard coat forming coating material before irradiating the active energy ray. In the preliminary drying, for example, the time required for the web to pass from the inlet to the outlet in the drying furnace set at a temperature of about 23 to 150 ° C., preferably 50 to 120 ° C. is about 0.5 to 10 minutes. , Preferably by passing at a line speed of 1 to 5 minutes.

When the active energy ray is irradiated in the step (2), the wet coating film made of the second hard coat forming coating material may be preheated to a temperature of 40 to 120 ° C, preferably 70 to 100 ° C. The coated film can be surely brought into a dry-to-touch state. The preheating method is not particularly limited, and can be performed by any method. An example of a specific method will be described later in the description of step (4) below.

In the step (3), the method for forming the wet coating film made of the first hard coat forming paint is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The wet coating film made of the first hard coat forming paint formed in the step (3) is completely cured in the step (4). At the same time, the coating film made of the second hard coat forming coating is also completely cured.

Although not intended to be bound by theory, it is possible to improve the adhesion between the first hard coat and the second hard coat by the method described above. Then, it is sufficient to make the coating film dry to the touch, but it is suppressed to an integrated light amount that is insufficient for complete curing, and an integrated light amount sufficient to completely cure the coating film for the first time in the above step (4). It is assumed that complete curing of both hard coats is achieved simultaneously.

In the step (4), the irradiation with active energy rays is preferably 240 mJ / cm ² or more from the viewpoint of complete curing of the coating film and the adhesion of the first hard coat and the second hard coat. the 320 mJ / cm ² or more, more preferably carried out so that 360 mJ / cm ² or more. On the other hand, in view to obtain a hard coat laminated film are prevented from becoming those yellowing, and from the viewpoint of cost, integrated light quantity 10000 mJ / cm ² or less, preferably 5000 mJ / cm ² or less, more preferably 2000 mJ / cm ² Perform as follows.

In the step (4), it is preferable to pre-dry the wet coating film made of the first hard coat forming paint before irradiating the active energy ray. In the preliminary drying, for example, the time required for the web to pass from the inlet to the outlet in the drying furnace set at a temperature of about 23 to 150 ° C., preferably 50 to 120 ° C. is about 0.5 to 10 minutes. , Preferably by passing at a line speed of 1 to 5 minutes.

When irradiating active energy rays in the step (4), the wet coating film made of the first hard coat forming paint has characteristics of the first hard coat forming paint and the second hard coat forming paint. From the viewpoint of obtaining good interlaminar adhesion strength even when the temperature is greatly different, the temperature is usually preheated to 30 to 100 ° C, preferably 40 to 85 ° C, more preferably 50 to 75 ° C. The preheating method is not particularly limited, and can be performed by any method. For example, as shown in FIG. 3, a method of controlling the surface temperature of the roll 8 to a predetermined temperature by holding the web 9 on the roll 8 facing the active energy ray irradiation apparatus 7; surrounding the active energy ray irradiation apparatus as an irradiation furnace And a method of controlling the temperature in the irradiation furnace to a predetermined temperature; and combinations thereof.

After the step (4), an aging process may be performed. The characteristics of the hard coat laminated film can be stabilized.

Goods:
Since the hard coat laminated film of the present invention has preferable characteristics as described above, it can be suitably used as an article or a member of an article. The article of the present invention is an article (including an article member) including the hard coat laminated film of the present invention. Examples of the article (including article members) include image display devices such as liquid crystal displays, plasma displays, and electroluminescent displays, and members such as display face plates, transparent conductive substrates, and housings; TVs, personal computers, tablet-type information devices, smartphones, and members such as housings and display faceplates; further refrigerators, washing machines, cupboards, clothes racks, and panels constituting them; windows and doors of buildings, etc. A vehicle, a vehicle window, a windshield, a roof window, an instrument panel, etc .; an electronic signboard and a protective plate thereof; a show window; a solar cell and a member such as a casing or a front plate thereof; .

When producing the article of the present invention, the front surface of the hard coat laminated film of the present invention (the surface that is normally viewed when the article is put into actual use) in order to impart high designability to the resulting article. The same applies hereinafter.) A decorative sheet may be laminated on the opposite surface. In such an embodiment, the hard coat laminated film of the present invention is a panel constituting the front of the door body that opens and closes the opening of the front of the main body of articles such as a refrigerator, a washing machine, a cupboard, and a clothes rack, and the main body. This is particularly effective when used as a panel constituting the flat surface of the lid that opens and closes the flat opening. The decorative sheet is not limited, and any decorative sheet can be used. As the decorative sheet, for example, any colored resin sheet can be used.

Examples of the colored resin sheet include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly (meth) acrylimide resins; polyolefins such as polyethylene, polypropylene, and polymethylpentene. Cellulosic resin: Cellulosic resin such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / propylene / styrene copolymer, styrene・ Styrene resins such as ethylene / ethylene / propylene / styrene copolymers and styrene / ethylene / butadiene / styrene copolymers; polyvinyl chloride resins; polyvinyl chloride Fluorine-containing resins such as polyvinylidene fluoride; other colors such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, polyethersulfone; A resin sheet can be raised. These sheets include an unstretched sheet, a uniaxially stretched sheet, and a biaxially stretched sheet. Moreover, the laminated sheet which laminated | stacked 1 or more types of these 2 or more layers is included.

The thickness of the colored resin sheet is not particularly limited, but may be usually 20 μm or more, preferably 50 μm or more, more preferably 80 μm or more. Further, from the viewpoint of meeting the demand for thinner articles, it may be usually 1500 μm or less, preferably 800 μm or less, more preferably 400 μm or less.

A printed layer may be provided on the front surface of the colored resin sheet to enhance the design feeling, if desired. The printing layer is provided for imparting high designability, and can be formed by printing an arbitrary pattern using an arbitrary ink and an arbitrary printing machine.

Printing is performed directly or via an anchor coat on the surface opposite to the front surface of the hard coat laminated film of the present invention, and / or on the front surface surface of the colored resin sheet. Can be applied in part. The patterns include metal-like patterns such as hairlines, wood grain patterns, stone patterns imitating the surface of rocks such as marble, fabric patterns imitating cloth and cloth-like patterns, tiled patterns, brickwork patterns, parquet patterns, And patchwork. As printing ink, what mixed the pigment, the solvent, the stabilizer, the plasticizer, the catalyst, the hardening | curing agent, etc. in the binder suitably can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamides. Resins such as resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used. Moreover, in order to give a metallic design, aluminum, tin, titanium, indium and oxides thereof are directly or via an anchor coat on the surface opposite to the front surface of the hard coat laminated film of the present invention. Alternatively, and / or on the front surface of the colored resin sheet, vapor deposition may be performed entirely or partially by a known method.

Lamination | stacking with the hard-coat laminated | multilayer film of this invention and the said decorative sheet is not restrict | limited, It can carry out by arbitrary methods. Examples of the method include a method of dry laminating using a known adhesive; and a method of forming a layer made of a known pressure-sensitive adhesive and then pressing them together.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measurement method (a) Falling ball impact test (falling ball impact resistance):
A sheet-like adhesive with a thickness of 25 μm (“836-1 (trade name)” manufactured by 3M Co., Ltd.) is bonded to the entire surface of one side of the float glass (thickness 3 mm) specified in JIS R3202: 2011 of Test Piece Co., Ltd. Further, the hard coat laminated film was bonded onto the surface so that the printed surface (the surface opposite to the first hard coat) became the bonding surface, and used as a test piece. 110 g of steel balls were freely dropped from a predetermined height onto the test surface (the first hard coat surface of the hard coat laminated film), and then the test piece was visually observed from the first hard coat surface side, When no trace of hitting with a steel ball was recognized, the test was accepted, and when the trace of hitting could be confirmed, it was rejected as a fine crack even though it was slight. Repeatedly passed The maximum was determined the height.

(B) Pencil hardness:
Except that the load was 1 kg, the first hard coat surface of the hard coat laminated film was measured according to JIS K 5600-5-4: 1999 using a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd.

(C) Water contact angle (initial water contact angle):
A method of calculating the first hard coat surface of the hard coat laminated film from the width and height of water droplets using an automatic contact angle meter “DSA20 (trade name)” manufactured by KRUS (see JIS R 3257: 1999). Measured with

(D) Scratch resistance (water contact angle after cotton wiping):
JIS L is a test piece that is 150 mm long and 50 mm wide and is sampled so that the machine direction of the hard coat laminated film is the vertical direction of the test piece so that the first hard coat of the hard coat laminated film is on the surface. A stainless steel plate (vertical 10 mm, horizontal 10 mm) placed on the Gakushin type testing machine of 0849: 2013 and covered with 4 layers of gauze (medical type 1 gauze from Kawamoto Sangyo Co., Ltd.) on the friction terminal of the Gakushin type testing machine , 1 mm thick), set so that the vertical and horizontal surfaces of the stainless steel plate are in contact with the test piece, put a 350 g load, and move the first hard coat surface of the test piece to the friction terminal moving distance 60 mm, speed 1 reciprocation / After rubbing back and forth 10,000 times under the condition of seconds, the water contact angle of the cotton swab was measured according to the method (c). When the water contact angle is 100 degrees or more, after reciprocating 5,000 times, according to the method of (c) above, the operation of measuring the water contact angle of the cotton wiping location was repeated and evaluated according to the following criteria: .
A: Water contact angle of 100 degrees or more even after 25,000 round trips.
B: Water contact angle is 100 degrees or more after 20,000 round trips, but less than 100 degrees after 25,000 rounds.
C: Water contact angle is 100 degrees or more after 15,000 round trips, but less than 100 degrees after 20,000 rounds.
D: Water contact angle is 100 degrees or more after 10,000 round trips, but less than 100 degrees after 15,000 rounds.
E: Water contact angle less than 100 degrees after 10,000 round trips.

(E) Total light transmittance:
According to JIS K 7361-1: 1997, it measured using the turbidimeter "NDH2000 (brand name)" of Nippon Denshoku Industries Co., Ltd.

(F) Yellowness index;
In accordance with JIS K 7105: 1981, the measurement was performed using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation.

(G) Cross cut test (adhesion):
In accordance with JIS K 5600-5-6: 1999, 100 square cuts (1 square = 1 mm × 1 mm) from the first hard coat surface side were put into the hard coat laminated film, and then the adhesion test tape was applied to the grid. After pasting and squeezing with fingers, it was peeled off. Evaluation criteria were in accordance with Table 1 of the above JIS standard.
Classification 0: The edges of the cuts are completely smooth, and there is no peeling in any lattice eye.
Classification 1: Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
Classification 2: The coating film is peeled along the edge of the cut and / or at the intersection. The cross-cut portion is clearly affected by more than 5% but not more than 15%.
Classification 3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
Classification 4: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 35% but not more than 65%.
Category 5: When the degree of peeling exceeds Category 4.

(H) Minimum bending radius:
JIS-K6902: With reference to the bending formability of 2007 (Method B), the test piece conditioned for 24 hours at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5% was bent at a temperature of 23 ° C. ± 2 ° C. The lines were formed in a direction perpendicular to the machine direction of the hard coat laminated film, and bent so that the first hard coat of the hard coat laminated film was on the outer side to form a curved surface. Among the forming jigs in which no cracks occurred, the radius of the front part of the smallest front part radius was defined as the minimum bending radius. This “front portion” means the same term relating to a forming jig in the method B defined in JIS K6902: 2007, section 18.2.

(Li) Cutting workability (state of curved cutting line):
Using a router machine that is automatically controlled by a computer, a hard-coated laminated film was provided with a true circular cutting hole with a diameter of 2 mm and a true circular cutting hole with a diameter of 0.5 mm. The mill used at this time was a four-blade made of cemented carbide with a rounded tip at the tip of the cylinder, with a nick, and the blade diameter was appropriately selected according to the machining location. Then, about the cutting hole of diameter 2mm, the cutting end surface was observed visually or a microscope (100 times), and the following references | standards evaluated. Similarly, about the cutting hole of diameter 0.5mm, the cutting end surface was observed visually or microscope (100 times), and the following references | standards evaluated. The table shows the former results-the latter results in this order.
A: No cracks or whiskers are observed even under microscopic observation. O: No cracks are observed even under microscopic observation. But beards are allowed.
(Triangle | delta): A crack is not recognized visually. However, cracks are observed by microscopic observation.
X: Cracks are recognized visually.

(Nu) Surface smoothness (surface appearance):
The surface (both surfaces) of the hard coat laminated film was visually observed while being applied with various incident angles of the fluorescent light, and evaluated according to the following criteria.
A: There is no wave or scratch on the surface. There is no cloudiness even when looking at the light up close.
○: There is a part with a slight cloudiness when looking closely at the light.
Δ: Slight swells and scratches are observed on the surface when viewed closely. There is also a cloudiness.
X: Many undulations and scratches can be observed on the surface. There is also a clear cloudiness

Raw materials used (A) Multifunctional (meth) acrylate:
(A-1) Dipentaerythritol hexaacrylate. It has 6 acryloyl groups in one molecule.
(A-2) Tripentaerythritol acrylate (having 8 or 7 acryloyl groups in one molecule) of Osaka Organic Chemical Industry Co., Ltd. 60% by mass, dipentaerythritol acrylate (6 or 5 in 1 molecule) 15% by mass, tetrapentaerythritol acrylate (having 10 or 9 acryloyl groups in one molecule), 10% by mass, polypentaerythritol acrylate (the number of connections is N (2N + 2)) Or a mixture of monopentaerythritol acrylate (having 4 or 3 acryloyl groups in one molecule) and “Biscoat # 802” (which has 1 or (2N + 1) acryloyl groups, N is a natural number of 5 or more). Product name)".
(A-3) Pentaerythritol triacrylate. It has 3 acryloyl groups in one molecule.

(B) Water repellent:
(B-1) An acryloyl group-containing fluoropolyether water repellent “KY-1203 (trade name)” from Shin-Etsu Chemical Co., Ltd. Solid content 20% by weight.
(B-2) Solvay's methacryloyl group-containing fluoropolyether water repellent “FOMBLIN MT70 (trade name)”. Solid content 70% by weight.

(C) Silane coupling agent:
(C-1) N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane “KBM-602 (trade name)” from Shin-Etsu Chemical Co., Ltd.

(D1) Polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule:
(D1-1) Pentaerythritol triacrylate. It has 3 acryloyl groups in one molecule.

(D2) a compound having two or more secondary thiol groups in one molecule;
(D2-1) Compound “Karenz MT NR-1 (trade name)” having three secondary thiol groups in one molecule of Showa Denko KK 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.
(D2-2) Compound “Karenz MT BD-1 (trade name)” having two secondary thiol groups in one molecule of Showa Denko KK 1,4-bis (3-mercaptobutyryloxy) butane.
(D2-3) “Karenz MT PE-1 (trade name)”, a compound having four secondary thiol groups in one molecule of Showa Denko KK Pentaerythritol tetrakis (3-mercaptobutyrate).

(D3) A group consisting of (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth) acrylate. One or more (meth) acrylates selected from:
(D3-1) “Evekril 284 (trade name)” by Daicel Ornex Co., Ltd. A mixture of 88% by mass of an aliphatic urethane acrylate having two acryloyl groups in one molecule and 12% by mass of 1,6-hexanediol diacrylate (having two acryloyl groups in one molecule).
(D3-2) “Evekril 4100 (trade name)” of Daicel Ornex Co., Ltd. An aliphatic urethane acrylate having three acryloyl groups in one molecule.
(D3-3) “Evekril 4200 (trade name)” of Daicel Ornex Co., Ltd. An aliphatic urethane acrylate having four acryloyl groups in one molecule.
(D3-4) “Art Resin UN-904 (trade name)” by Negami Kogyo Co., Ltd. Urethane acrylate having 10 acryloyl groups in one molecule.
(D3-5) Tricyclodecane dimethanol diacrylate “A-DCP (trade name)” of Shin-Nakamura Chemical Co., Ltd. It has two acryloyl groups in one molecule.
(D3-6) Acrylic acid adduct “Epoxy ester 70PA (trade name)” of tripropylene glycol diglycidyl ether of Kyoeisha Chemical Co., Ltd. It has two acryloyl groups in one molecule.
(D3-7) Acrylic acid adduct “epoxy ester 80MFA (trade name)” of glycerin diglycidyl ether of Kyoei Chemical Co., Ltd. It has two acryloyl groups in one molecule.
(D3-8) 1,6-hexanediol diacrylate. It has two acryloyl groups in one molecule.
(D3-9) 2-acryloyloxyethyl-succinic acid. It has one acryloyl group in one molecule.
(D3-10) Hydroxyethylacrylamide. It has one acryloyl group in one molecule.

(E) Inorganic fine particles having an average particle diameter of 1 to 300 nm:
(E-1) Silica fine particles having an average particle diameter of 20 nm and surface-treated with a silane coupling agent having a vinyl group.

(F) Leveling agent:
(F-1) Silicon-acrylic copolymer leveling agent “DISPARON NSH-8430HF (trade name)” from Enomoto Kasei Co., Ltd. Solid content 10% by weight.

(G) Optional component:
(G-1) An acetophenone photopolymerization initiator (1-hydroxy-cyclohexyl-phenylketone) “IRGACURE184 (trade name)” manufactured by BASF.
(G-2) 1-methoxy-2-propanol.

(H1) First hard coat forming paint:
(H1-1) 100 parts by mass of (A-1), 2 parts by mass of (B-1) (0.40 parts by mass in terms of solid content), 0.06 parts by mass of (B-2) (in terms of solid content) 0.042 parts by mass), 0.5 parts by mass of (C-1), 4 parts by mass of (G-1), and 100 parts by mass of (G-2).
(H1-2) 100 parts by mass of (A-2), 2 parts by mass of (B-1) (0.40 parts by mass in terms of solid content), 0.06 parts by mass of (B-2) (in terms of solid content) 0.042 parts by mass), 0.5 parts by mass of (C-1), 4 parts by mass of (G-1), and 100 parts by mass of (G-2).
(H1-3) 100 parts by mass of (A-3), 2 parts by mass of (B-1) (0.40 parts by mass in terms of solids), 0.06 parts by mass of (B-2) (in terms of solids) 0.042 parts by mass), 0.5 parts by mass of (C-1), 4 parts by mass of (G-1), and 100 parts by mass of (G-2).
(H1-4) 100 parts by mass of (A-1), 2 parts by mass of (B-1) (0.40 parts by mass in terms of solid content), 0.06 parts by mass of (B-2) (in terms of solid content) 0.042 parts by mass), (C-1) 0.5 parts by mass, (E-1) 20 parts by mass, (G-1) 4 parts by mass, and (G-2) 130 parts by mass. Paint obtained by mixing and stirring.

(H2) Second hard coat forming paint:
(H2-1) 50 parts by mass of (d1-1), 25 parts by mass of (d2-1), 25 parts by mass of (d3-1), 200 parts by mass of (E-1), and (F-1) ) A paint obtained by mixing and stirring 2 parts by mass (0.2 parts by mass in terms of solid content), 15 parts by mass of (G-1), and 280 parts by mass of (G-2). Table 1 shows the composition. In addition, the said component (F-1) has described the value of solid content conversion in the table | surface.

(H2-2 to 31) A paint obtained in the same manner as (H2-1) above, except that the composition of the paint was changed as shown in any one of Tables 1 to 7. The formulation is shown in any one of Tables 1-7. In addition, the said component (F-1) has described the value of solid content conversion in the table | surface.

(P) Transparent resin film:
(P-1) Two-type, three-layer, multi-manifold co-extrusion T-die 11, a first mirror roll (a roll on the side of holding the molten film 12 and feeding it to the next transfer roll) 13 and a second mirror roll 14 And an apparatus (see FIG. 4) equipped with a winder equipped with a mechanism for pressing the molten film 12 as an outer layer (α1 layer and α2 layer) of a two-kind three-layer multilayer resin film. Poly (meth) acrylimide “PLEXIMID TT50 (trade name)” is used as an intermediate layer (β layer) and aromatic polycarbonate “Caliver 301-4 (trade name)” of Sumika Stylon Polycarbonate Co., Ltd. Are co-extruded continuously from the first mirror surface roll 13 and the second mirror surface roll 14 so that the α1 layer is on the first mirror surface roll 13 side. 250 [mu] m, the layer thickness 80μm of α1 layers, layer thickness 90μm of the β layer to obtain a transparent resin film layer thickness 80μm of α2 layers. At this time, the setting conditions were a T die setting temperature of 300 ° C., a first mirror surface roll setting temperature of 130 ° C .; a second mirror surface roll setting temperature of 120 ° C., and a take-up speed of 6.5 m / min.

(P-2) As both outer layers, instead of the above “PLEXIMID TT50 (trade name)”, the total of structural units derived from the polymerizable monomer is 100 mol%, and the structural unit derived from methyl methacrylate is 76.8 mol. % And a transparent resin film was obtained in the same manner as in the above (P-1) except that an acrylic resin containing a structural unit derived from vinylcyclohexane in an amount of 23.2 mol% was used.

Example 1
Corona discharge treatment was performed on both sides of (P-1). The wetness index on both sides was 64 mN / m. Next, the above (H2-1) was applied on the surface of the α1 layer side so as to have a wet thickness of 40 μm (thickness after curing: 22 μm) using a die-type coating apparatus. Next, after passing the drying furnace set at a furnace temperature of 90 ° C. at a line speed that takes 1 minute to pass from the inlet to the outlet, the high-pressure mercury lamp type ultraviolet irradiation device 7 and a diameter of 25.4 cm are passed. The mirror surface metal roll 8 was used (see FIG. 3), and the mirror surface metal roll 8 was processed at a temperature of 90 ° C. and an integrated light amount of 80 mJ / cm ² . The wet coating film of (H2-1) was a touch-dried coating film. Next, using a die-type coating apparatus on the (H2-1) touch-dried coating film, the (H1-1) is made to have a wet thickness of 4 μm (post-curing thickness: 2 μm). Applied. Next, after passing the drying furnace set at a furnace temperature of 80 ° C. at a line speed that takes 1 minute to pass from the inlet to the outlet, the high-pressure mercury lamp type ultraviolet irradiation device 7 and a diameter of 25.4 cm are passed. The first hard coat and the second hard are processed using a curing device in which the mirror surface metal roll 8 is opposed to each other (see FIG. 3), and the mirror surface metal roll 8 is processed at a temperature of 60 ° C. and an integrated light quantity of 480 mJ / cm ^2. A coat was formed. Subsequently, the third hard coat is applied on the surface of the α2 layer side, and the same paint as that used for forming the second hard coat (Example 1 is (H2-1) above) is used to apply the die method. Using the apparatus, it was formed so as to have the same thickness after curing as in the second hard coat (Example 1 had a thickness after cure of 22 μm) to obtain a hard coat laminated film. The above tests (i) to (nu) were conducted. The results are shown in Table 1.

Examples 2-31
The same procedure as in Example 1 was performed except that the second hard coat-forming coating material used was any one shown in Tables 1-7. The results are shown in any one of Tables 1-7.

Example 32
The same procedure as in Example 1 was performed except that the above (H1-2) was used as the first hard coat-forming coating material. The results are shown in Table 7.

Example 33
The same operation as in Example 1 was conducted except that the above (H1-3) was used as the first hard coat-forming coating material. The results are shown in Table 7.

Example 34
The same operation as in Example 1 was conducted except that the above (H1-4) was used as the first hard coat-forming coating material. The results are shown in Table 7.

Example 35
It carried out like Example 1 except having used said (P-2) as a transparent resin film. The results are shown in Table 7.

The hard coat laminated film of the present invention is excellent in falling ball impact resistance. The preferred hard coat laminated film of the present invention is excellent in falling ball impact resistance, surface hardness, scratch resistance, transparency, color tone, interlayer adhesion strength, bending resistance, cutting workability, and surface appearance. Therefore, the hard coat laminated film of the present invention is a member of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display (including an image display device having a touch panel function and an image display device not having a touch panel function). In particular, it can be suitably used as a display face plate of a smartphone or tablet terminal.

It is a conceptual diagram of the section which shows an example of the hard coat lamination film of the present invention. It is a figure explaining a curvature radius. It is a conceptual diagram which shows an example of an ultraviolet irradiation device. It is a conceptual diagram which shows an example of a film forming apparatus.

1: First hard coat 2: Second hard coat 3: First poly (meth) acrylimide resin layer (α1)
4: Aromatic polycarbonate resin layer (β)
5: Second poly (meth) acrylimide resin layer (α2)
6: Third hard coat 7: Ultraviolet irradiation device 8: Mirror surface metal roll 9: Web 10: Holding angle 11: Coextrusion T die 12: Molten film 13: First mirror surface roll 14: Second mirror surface roll

Claims (14)

The first hard coat, the second hard coat, and the transparent resin film layer in order from the surface side,
The first hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(D) 100 mass parts of polymerizable compound; and (E) 50-300 mass parts of inorganic fine particles having an average particle diameter of 1-300 nm;
Made of paint containing;
Here, the polymerizable compound (D) is
(D1) Polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule 60 to 30% by mass;
(D2) 5 to 70% by mass of a compound having two or more secondary thiol groups in one molecule; and
(D3) A group consisting of (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth) acrylate. One or more (meth) acrylates selected from 0 to 50% by weight;
Consists of;
The sum of the component (d1), the component (d2), and the component (d3) is 100% by mass;
Hard coat laminated film.
The first hard coat, the second hard coat, and the transparent resin film layer in order from the surface side,
The first hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(D) 100 mass parts of polymerizable compound; and (E) 50-300 mass parts of inorganic fine particles having an average particle diameter of 1-300 nm;
Made of paint containing;
Here, the polymerizable compound (D) is
(D1) a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule; and
(D2) a compound having two or more secondary thiol groups in one molecule;
Hard coat laminated film consisting of
The hard coat laminated film according to claim 1 or 2, wherein the component (d2) contains a compound having 2 or 3 secondary thiol groups in one molecule.
The hard coat laminated film according to claim 1, wherein the amount of the component (d3) in the polymerizable compound (D) is 5 to 50% by mass.
The first hard coat, the second hard coat, and the transparent resin film layer in order from the surface side,
The first hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(D) 100 mass parts of polymerizable compound; and (E) 50-300 mass parts of inorganic fine particles having an average particle diameter of 1-300 nm;
Made of paint containing;
Here, the polymerizable compound (D) is
(D1) a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule;
(D2) a compound having two or more secondary thiol groups in one molecule; and
(D3) A group consisting of (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth) acrylate. One or more (meth) acrylates selected from:
Hard coat laminated film consisting of
The hard coat laminated film of Claim 4 or 5 in which the said component (d3) contains the aliphatic urethane (meth) acrylate which has two (meth) acryloyl groups in 1 molecule.
The hard coat laminated film according to claim 4 or 5, wherein the component (d3) contains tricyclodecane dimethanol di (meth) acrylate.
The hard coat laminated film according to any one of claims 4 to 7, wherein the component (d2) contains a compound having 2 or 3 secondary thiol groups in one molecule.
The first hard coat, the second hard coat, and the transparent resin film layer in order from the surface side,
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a paint containing inorganic fine particles;
A hard coat laminated film satisfying the following characteristics (a) and (b).
(I) The surface opposite to the first hard coat surface of the hard coat laminated film and the float plate glass are bonded, and a steel ball having a mass of 110 g is freely dropped from a height of 30 cm onto the first hard coat surface. When visually observed from the first hard coat surface side, no trace of striking with a steel ball is observed.
(B) The pencil hardness of the surface of the first hard coat measured in accordance with JIS K 5600-5-4: 1999 is 3H or more except that the load is 1 kg.
The second hard coat is
(D1) a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule;
(D2) a compound having two or more secondary thiol groups in one molecule; and
(E) Inorganic fine particles having an average particle size of 1 to 300 nm;
The hard coat laminated film according to claim 9, comprising a paint containing
The second hard coat is
(D1) a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule;
(D2) a compound having two or more secondary thiol groups in one molecule;
(D3) A group consisting of (meth) acrylate having two (meth) acryloyl groups in one molecule, (meth) acrylate having one (meth) acryloyl group in one molecule, and urethane (meth) acrylate. One or more (meth) acrylates selected from: and
(E) Inorganic fine particles having an average particle size of 1 to 300 nm;
The hard coat laminated film according to claim 9, comprising a paint containing
Furthermore, the hard-coat laminated film of any one of Claims 9-11 which satisfy | fills the following characteristics (c) and (d).
(C) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(D) The water contact angle after 20,000 cotton swabs on the first hard coat surface is 100 degrees or more.
The image display apparatus containing the hard-coat laminated | multilayer film of any one of Claims 1-12.
An article comprising the hard coat laminated film according to any one of claims 1 to 12.